Carbamoyl oximes

ABSTRACT

THEIR MANUFACTURE AND FUNGICIDAL AND VIRUCIDAL ACTIVITY ARE DISCLOSED. In this formula R1 stand for alkylidene, aralkylidene or mono-, bi- or tricycloalkylidene and R2 stands for C8 to C14 alkyl, mono- or bicycloalkyl or cycloalkenyl.   Carbamoyl oximes of the formula

Umted States Patent 11 1- 1111 3,843,724 Gatzi Oct. 22, 1974 1 CARBAMOYL OXIMES 3,299.137 H1967 Payne et al 260/566 AC 5] Inventor: a Gatzi, Basel, Switzerland 3,479,40 11/1969 Payne et a1 260/566 AC [73] Assignee: ClBA-GEIGY Corporation, Ardsley, Primary Examiner-Leon Zitver NY. Assistant Examiner-Gerald A. Schwartz [22] Filed. Mar 15 1971 Attorney, Agent, or Firm-Harry Falber; Frederick H.

' Rabin [21] Appl. No.: 124,527

[57] ABSTRACT [30] Foreign Application Priority Data Carbamoyl oximes of the formula Jan. 14, 1971 Switzerland 4. 4319/70 R1=NO-C-NHR11 [52] US. Cl 260/566 AC, 424/327 I [51] Int. Cl. C07c 131/02 W V s [58] Field of Search 260/566 AC manufacture and funglcldal and actlvlty are disclosed. In this formula R stand for alkylidne,

' 5 References Cited aralkylidene or mono-, bior tricycloalkyliclene and R UNITED STATES PATENTS stands for C to C alkyl, monoor bicycloalkyl or cy- 3,063,823 11/1962 14111118 et a1 7. 260/566 AC Cloalkenyl' 3,231,599 H1966 Kilsheimer et a1. 260/566 AC 3 Claims, No Drawings wherein R, represents an alkylidene radical having optionally substituted by alkoxy, an aralkylidene radical, an optionally loweralkylsubstituted cycloalkylidene, bicycloalkylidene, or tricycloalkylidene radical,

R represents an alkyl radical having eight to fourteen carbon atoms, an optionally lower-alkylsubstituted cyloalkyl, cycloalkenyl, or bicycloalkyl radical. ln Formula I, R stands for hydrocarbon radicals having a bivalent carbon. atom. In the case of alkylidene radicals, this bivalent C-atom is always the intermediate member; in the case of aralkylidene radicals, it can be either the intermediate member or the end member of the aliphatic chain. Alkylidene radicals are branched or straight-chain, and have three to nine carbon atoms in the chain. Such an alkylidene radical can be substituted by one or several lower alkoxy radicals containing one to four carbon atoms, such as, e.g., methoxy, ethoxy,

propoxy and isopropoxy. The aliphatic part of an aralk ylidenc radical has one to five carbon atoms; and phenyl or phenyl substituted by halogen or low alkyl such as e.g., chlorine, bromine and/or methyl constitutes the aryl part. Cycloalkylidene radicals R contain five to twelve carbon atoms as ring members, and can carry alkyl radicals as substituents, especially low alkyl containing one to four carbon atoms, e.g., methyl and/or isopropyl radicals. As cycloalkylidene radicals, radicals of ,cyclopentane, cyclohexane and cyclododecane are preferred. With respect to the bicycloalkylidene radicals, these are, in particular, radicals of bicyclic ter penes; and by tricycloalkylidene radicals is meant especially a tricycloheptylidene radical. By an alkyl radical R having eight to fourteen carbon atoms is meant, in particular, a straight-chain radical such as, e.g., the noctyl, n-decyl, n-dodecyl and n-tetradecyl radical. Mentioned as cycloalkyl and cycloalkenyl radicals are particularly the cyclohexyl and cyclohexenyl radicals, which can carry as substituents lower alkyl radicals containing one to four carbon atoms, preferably methyl and/or isopropyl radicals. A bicycloalkyl radical R is preferably a bicycloheptyl radical, e.g., the bicyclo [4.1.0] heptyl radical, or a radical of a bicyclic terpene, such as'a radical of bornane, of norbornane or of 1,3,3- trimethylbornane.

The new carbamoyloximes of Formula I are produced according to the present invention by reacting an oxime of Formula II:

.a. with an isocyanate of Formula Ill:

R NCO optionally in the presence of a catalyst, or

b. with a carbamic acid halide of Formula IV:

Hal (:0 NRH,

in the presence of an acid-binding agent, or

c. with the formation components of a carbamic acid halide, namely, phosgene and an amine of Formula V:

NH R

in the presence of an acid-binding agent.

In Formulae II to V, the symbols R and R have the meanings given under Formula I; in Formula lV, Hal

stands for chlorine or bromine.

Instead of an isocyanate of Formula III or a carbamic acid'halide of Formula IV, it is possible to use for the process according to the invention. also the mixture of anisocyanate of Formula Ill and the corresponding carbamic acid halideof Formula IV.

The reactions according to the invention are performed in the presence of acid-binding agents, such as inorganic bases, e.g., hydrides, hydroxides and carbonates of alkali metals and alkalineearth metals; or organic nitrogen bases, e.g., tertiary amines such as pyridine, triethylamine, dimethylaniline, etc. Furthermore, as catalysts for the reaction with the isocyanates of Formula III are used, e.g., tertiary amines or organotin compounds. It is preferable to perform the reactions in solvents or diluents inert to the reactants, e.g., in ethers or ethereal compounds such as diethylether, dipropylether, dioxane, tetrahydrofuran; in amines such as N,N-dialkylated carboxylic acid amides; as well as in halogenated hydrocarbons, or aliphatic oraromatic hydrocarbons.

The newcarbamoyloximes are obtained using the process according to the invention in good to very good yields. They are soluble and stable in the usual organic solvents.

it is known that oximes can exist in two stereoisomeric forms: the synand anti-form. The carbamoyloximes of Formula I too exist in these two forms. Accordingly, the term carbamoyloximes of Formula I in the case of the present invention covers both stereoisomeric forms.

The starting materials of Formula II used for the reactions according to the invention are known compounds and can be produced by known methods.

The new carbamoyloximes of .Formula I have an excellent fungicidal and viricidal action on numerous phytophatogenic fungi and viruses respectively. As phytopathogenic fungi, e.g., mildew fungi such as the powdery mildew of cucumbers Erysiphe cichoracearum), powdery mildew of apples Podosphaera leucolricha), powdery mildew of roses (Sphaerotheca pannosa), powdery mildew of wheat (Erysiphe graminis); as well as downy mildew fungi, such as the one causing the blight on leaves and tubers of potatoes (Phytophthora infestans); downy mildew of vines Plasmophora viticola); also leaf spot fungi such as those causing the grey speck disease of tomatoes Alternaria solani), leaf spot of -celery Septoria spicola); and rust fungi such as bean rust( Uromyces appendiculatus); also grey mould Botrytis cinera) which is very difficult to control, etc., may be mentioned. As phytopathogenic viruses -the following may for example be mentioned; bacilliform viruses as for example the tobacco mosaic virus or the potato-M-virus, filiform viruses as for example the potato-Y-virus or the carrot yellowing virus and spheroidal viruses as for example the cucumber mosaik virus. In addition to a persistent action, the compounds also have a good curative effect, so that even fungi and viruses which have already penetrated into the plant tissue are killed off by application of the new compounds.

Moreover, various carbamoyloximes of Formula I also possess insecticidal and acaricidal properties. Since the compounds are not phytotoxic and have a favourable toxicity with regard to warm-blooded animals, they are most suitable for the protection of plants.

Preferred compounds of the invention are carbamoyloximes having the formula VI wherein R represents a mono or bicyclic alkylidene radical containing five to seven carbon atoms optionally substituted by a low alkyl group, a straight chained alkyl group containing three to nine carbon atoms optionally substituted by a low alkoxy group or a 'phenyl-low-alkylidene radical optionally halogen- I substituted and R represents a cycloalkenylmonoor bicyclicalkylradical with five to seven carbon atoms optionally substituted by a low alkyl group or a straight chained alkyl group containing eight to twelve carvbon atoms whereby low alkyl, low alkoxy and halogen have the meanings given above. In the group of'co'mpounds having the Formula VI the compounds of the formula VII are especially noteworthy.

In Formula Vll R represents a cyclopentylidene, cyclohexylidene, cycloheptylidene, l,4-menthylidene(3), bornylidcnc, norbornylidcne, S-nonylidene, butylidene, l,l-dimcthoxybutylidenc, benzylidenc, pchlorobenzylidene, phcnyl-l-cthylidene or phenyll-propylidene group and R represents a dodecyl, cyclohexyl, l,4-menthyl( 3),

- 3,5,5-trimethylcyclohexen( 2)-yl, bornyl or 1,3,3-trimethylnorbornyl group.

Fungicidal and viricidal agents according to the invention are produced in a manner known per se by the intimate mixing and grinding of active substances of the general Formula I with suitable carriers, optionally with the addition of dispersing agents or solvents which are inert to the active substances. The active substances can be used for the production of dusting agents, scattering agents, granulates, coated granulates, impregnated granulates, homogeneous granulates, wettable powders, pastes, emulsions, solutions, or aerosols.

Solid preparations (dusting agents, scattering agents, granulates) are produced by mixing together the active substances with solid carriers. The particle size of the carriers for dusting agents is advantageously up to ca. 0.1 mm, for scattering agents ca. 0.075 to 0.2 mm, and for granulates 0.2 mm or more. The concentration of active substances in the solid preparation is, as a rule 0.01 95 preferably 0.5 to percent. To these mixtures may also be added additives stabilising the active substance, and/or non-ionic, anion-active, and cationactive substances which, for example, improve the adhesiveness of the active substances on plants and parts of plants (adhesives and agglutinants), and/or ensure a higher degree of wettability wetting agents) and also of dispersibility (dispersing agents). The amounts in which these agents are employed are chosen such that the applied quantity of active substance is between 0.5 and I0 kg/hectare.

Water-dispersible active substance concentrates, wettable powders, pastes and emulsion concentrates constitute agents which can be diluted with water to obtain any desired concentration. They consist of active substance, carrier, surface-active substances, and

anti-foaming agents. and, optionally, solvents. The active substance concentration in these agents is 5-80 percent. The wettable powders and the .pastes are obtained by mixing and grinding the active substances with dispersing agents and pulverulent carriers, in suitable devices, until homogenity is obtained. It is advan tageous in some cases to use mixtures of different carri ers. Suitable anti-foaming agents are, e.g., silicones. The active substances are mixed, ground, sieved and filtered with the above mentioned additives in such a manner that in the case of the wettable powders the solid part does not exceed a particle size of 0.02 to 0.04 mm., and in the case of the pastes a particle size of 0.003 mm. Used for the production of emulsion concentrations and pastes are dispersing agents, organic solvents, and water. The solvents must be practically without smell; they must also be inert to the active substances, not phytotoxic, and not readily combustible.

Furthermore, the agents according to the invention can be used in the form of solutions. For this purpose the active'substance or several active substances of the general Formula I is or aredissolved in suitable organic solvents, mixtures of solvents, or water. The solutions are to contain the active substances in a concentration range of 1 20 percent. To the described agents according to the invention can be added other biocidal active substances or agents. The new agents can thus contain, in addition to the stated compounds of the general Formula I, and other fungicides, e.g., insecticides, herbicides, bactericides, fungistatica, bacteriostatica, or nematocides, for the purpose of widening the range of action of the new agents. The agents according to the invention may also contain fertilisers, trace elements, etc.

As active substances which may be mixed with the compounds of the invention the following may be mentioned among others:

Inorganic substances Elemental sulphur, ammonium polysulphide, sodium polysulphide, barium polysulphide, calcium polysulphide and calcium thiosulphate (lime sulphur), calcium hypochlorite, boric acid, sodium tetraboratedecahydrate (borax), zinc chloride, magnesium borate, nickel sulphate, potassium chromate, lead arsenate, cadmium chloride, and cadmium carbonate; Copper substances Copper (1) oxide (cuprous oxide), Bordeaux mixture, copper (II) sulphate-pentahydrate (copper sulphate), basic copper (II) chloride (copper oxychloride), copper (II) phosphate, tribasic copper (II) sulphate tribasic copper sulphate), basic copper (II) carbonate, copper (II) dihydrazine sulphate, a copperamine complex, copper II) sulphate/ammonium carbonate mixture, copper II) chloride/basic copper II) sulphate mixture, basic copper II) carbonate/zinc salt mixture, copper (ID-zinc chromate complex (copper zinc chromate), copper II)-zinc-cadmium-calcium chromate complex, copper (II) salt of oleic acid copper oleate), a copper II) salt of a fatty acid, copper II) salt of naphthenic acid (copper naphthenate), copper II) salt of 8-hydroxyquinoline oxine copper), copper I II) salt of 1,2-naphthoquinoneoxime-( 2), and copper ll) salt of 3-phenylsalicylate; Tin and mercury substances Bis-(tri-n-butyl tin)oxide, triphenyl tin hydroxide (fentin hydroxide), triphenyl tin acetate (fentin acetate), bis-( tributyl tin)succinate, mercury (I) chloride (calomel), mercury (II) chloride (mercuric chloride), mercury (II) oxide, mercury-zinc chromate complex, mercury II) lactate, ethylmercury chloride, 2- hydroxyethyl mercury acetate, ethylmercury isothiocyanate, 3-ethoxypropyl mercury bromide, chloromethoxypropyl mercury acetate, methoxyethyl mercury chloride, Z-methoxyethyl mercury silicate, bis-( methylmercury) sulphate, bis(methylmercury) ammonium acetate, ethylmercury acetate, 2-methoxyethylmercury acetate, ethylmercury phosphate, isopropylmethylmercury acetate, methylmercury cyanide, methylmercury benzoate, N-cyano-NI methylmercury) guanidine, methylmercury pentachlorophenolate, ethylmercury-2,3- dihydroxypropyl mercaptide, methylmercury-8- hydroxyquinolate (Ortho LM), N-(methyl-mercury)- 1,4,5,6,7,7-hexachlorobicyclo[2,2,1]hept-5-ene-2,3- dicarboximide, N( ethylmercury)-l,4,5,6,7,7- hexachlorobicyclo[2,2, l ]hept-5-ene-2,3- dicarboximide, sodium salt of ethylmercury thiosalicy late, N-( ethylmercury)-para-toluenesulphonic acid ani lide, phenylmercury acetate (PAM), phenylmercury propionate, phenylmercury triethanol-ammonium lactate (PAS), phenylmercury urea, N-(phenylmercury)- 1,4,5 ,6,7,7-hexachlorobicyclo[ 2,2,1 ]hept-5-ene-2,3- dicarboximide, phenylmercury dimethyldithiocarbamate, phenylmercury formamide, phenylmercury chloride, phenylmercury acetate, phenylmercury benzoate, phenylmercury borate, phenylmercury hydroxide, phenylmercury iodide, basic phenylmercury nitrate, phenylmercury monoethanolamine lactate, phenylmercury salicylate, hydroxymercury chlorophenol, hydroxymercury trichlorophenol, hydroxymercury nitrophenol, N-phenylmercury ethylenediamine, phenylmercury monoethanolammonium acetate, pyridylmercury acetate, hydroxyquinolate, a mercury II) complex with an organic phosphate, mixture of methylmercury-2,3- dihydroxypropylmercaptide and methylmercury acetate, mixture of hydroxymercury chlorophenol and hydroxymercury nitrophenol, and mercury-cadmium organic complex; Further organic metal compounds diphenylmercury-8-' Cadmium succinate, cadmium-di-n-propylxanthogenate, cadmium 8-hydroxyquinolate, phenylaminocadmium acetate, phenylaminocadmium dilactate, methylarsine sulphide, zinc octate and zinc oleate; Simple organic compounds aliphates) Formalin, paraformaldehyde, acrolein, methyl bromide, methyl isothiocyanate, tetraiodoethylene, 1,3- dichloropropene and related chlorinated C hydrocarbons, 1-chloro-3-bromopropene( l trans-1,4- dibromobutene( 2 l,3-dichloropropene( 1 l-chloro- 2-nitropropane, 2-chloro-l-nitropropane trichloronitromethane, dichlorotetrafluoro-acetone, sodium salt of propionic acid, calcium salt of propionic acid, chlo rofumaric acid-bis-fi-chloroethyl ester, sorbic acid and the potassium salt thereof, 2-propene-1,l-diolacetate, Z-aminobutane, dodecylguanidine acetate (dodine), dodecylquanidine phthalate, a-chloroacetyl-1,3- aminopropionitrile, a-bromoacetylvalinamide, 1,2- dichloro-1-( methylsulphonyl) ethylene, 1,2-dichloro- 1-(butylsulphonyl)ethylene, and trans 1,2-bis-(npropylsulphonyl)ethylene;

Benzene derivatives Para-dichlorobenzene, hecta-chlorobenzene HCB), 1 ,2,4,5-tetrachloro-4-nitrobenzene: tecnazene), Pentachloronitrobenzene quiritozene 1,3,5-trichloro- 2,4,6-trinitrobenzene, isomer mixture of 1,3,4- trichloro-2,6-dinitrobenzene and l,2,3-trichloro-4,6 dinitrobenzene, 2,4,5,6-tetrachloroisophthalic acid nitrile, 2,4-dinitrophenylthiocyanate, diphenyl, orthonitrodiphenyl, l-chloro-2,4-dinitronaphthalene, acenaphthene; Phenols 2,4,6-trichlorophenol, 2,4,5-trichlorophenol, 2,4,5- trichlor phenyl acetate, 2,4,5-trichlorophenyl chloroacetate, trichlorophenol zinc salt, meta-cresyl acetate, 2,3,4,6-tetrachlorophenol, pentaclhlorophenol (PCP), ortho-dihydroxybenzene, 2 ,4-dihydroxy-nhexylbenzene, Z-phenylphendl (ortho-phenylphenol), 3,5-dibromosalicylic aldehyde, 2-benzyl-4- chlorophenol, 2,2 '-dihydroxy-5 ,5 dichlorodiphenylmethane dichlorophene), dihydroxy-3 ,3 ',5,5 ',6,6'-hexachlorodiphenylrnethane, 2 ,2 '-dihydroxy-5 ,5 '-dichlorodiphenylsulphide, 2 ,2 dihydroxy-3 ,3 ',5 ,5 '-tetrachlorodiplilenylsulphide, 2,2

dihydroxy-3 ,3 ',5 ,5 '-tetrachlorodiphenylsulphide disodium salt, 4-chloro-orthophenylphenol, 1,4-dichloro- 2,5-dimethoxybenzene, salicylic anilide, bismuthsalicylate, trifluoromethylsalicylic anilide halogenatedwith chlorine or bromine, brominated salicylic anilide, an 3,5-dimethyl-4-chlorophenoxy)-ethanol; Dinitrophenol derivatives v 2-( l-methyl-n-propyl)-4,6-dinitrophenyl-2 methylcrotonate binapacryl), 2-( l-methyl-n-propyD- 4,6-dinitrophenylisopropylcarbonate dinobuton), 2-' l-methyl-n-heptyl )-4,6-dinitrophenylcrotonate dinocap), methyl-2,6-dinitro-4-( l-ethylhexyl)phenylcarbonate methyl-2,6-dinitro-4-( l-propylphenyDphenylcarbonate dinocton p), 4-nor'1yl-2,6-dinitrophenyl' butyrate, and S-methyl-2-( l-methyl-n-heptyl)-4,6- dinitrophenylthiocarbonate; Aniline derivatives 2,6-dichloro-4-nitroaniline (1 dichloran), 2- cyanoethyl-N-phenylcarbamate, propynyl-N- phenylcarbamate, and a-( 2 bromb;acetoxy)-actanilide;

Quinone derivatives dicarboximide 7 2,3,5 ,6-tetrachlorobenzoquinone( 1,4) chloranil), 2,3-dichloronaphthoquinonel 1,4) dichlone), 2- amino-3-chloronaphthoquinone( 1,4), 2,3,6,7-

Organic phosphates 0,0,0-trimethylthiophosphate, 0,0- diethylphthalimidophosphonothioate, 5-amino-bisdimethylamido)phosphinyl-3-phenyl-1 ,2,4-triazole triamiphos), S-methylamino-bisdimethylamido)phosphinyl-3-phenyl-l ,2,4-triazole, 0,0-diethyl-O-2-pyrazinylphosphorthioate, -ethyl-S,S- diphenyldithiolphosphate, O-ethyl-S-benzylphenyldithiophosphonate, and 0,0-diethyl-S-benzylthiolphosphate;

Dithiocarbamates Zinc salt of dithiocarbazine acid, sodium-N- methyldithiocarbamate metham), sodium-N- methoxyethyldithiocarbamate, sodium-N,N-

dimethyldithiocarbamate (DDC), ammonium-N,N- dimethyldithiocarbamate, zinc-N,N-dimethyldithiocarbamate (zirarn), iron-N,N-dimethyldithiocarbam'ate (ferbam), copper-N,N-dimethyldithiocarbamate, disodium-ethylene-l ,2-bis-dithiocarbamate nabam) zincethylene-1,Z-bis-dithiocarbamate zineb), ironethylene-l ,Z-bis-dithiocarbamate, m'anganese( II)- ethylenel ,Z-bis-dithiocarbamate maneb), calciumethylene-l ,2-bis-dithiocarbamate, ammoniumethylenel ,2-bis-dithiocarbamate, zinc-propylene-l ,2- bis-dithiocarbamate mezineb) propineb), bis( dimethylthiocarbamyl) ethylenel ,2-bisdithiocarbamate, complex consisting of (maneb) and zinc salt mancozeb),tetra-ethylthiuram monosulphide, bis-( N,N-dimethyldithiocarbamylrnercapto)- methylarsine, tetramethylthiuramdisulphide (thiram), dipyrrolidylthiuramdisulphide, N,N'-bis- (dimethylamino)thiuramdisulphide polyethylenethiuramsulphide, and complex consisting of (zineb) and polyethylenethiuramdisulphide (metiram); O-Heterocycles Bis-( 3,4-dichloro-2( )-furanoyl)ether mucochloric anhydride 2-methoxymethyl-5-nitrofuran, S-nitrofurfuraldoxime-( 2), 5-nitrofurfurylamideoxime-(2), and l-hydroxy-3 -acetyl-6-methylcyclohexene-( 5 )-dione- (2,4) dehydroacetic acid); l-N-Heterocycles 3-[2-( 3,5-dimethyl-2-hydroxycyclohexyl)-2-hydroxyethyl]-glutarimide (cycloheximide), phthalimide, pyridine-Z-thiol-l-oxide or l-hydroxypyridine-2- thione, zinc salt of pyridine-Z-thiol-l-oxide, manganese( I) salt of pyridine-Z-thiol-l-oxide, S-Hloxido-2-pyridyl)isothiuronium chloride a,a-bis(4- chlorophenyl)-3-pyridinemethanol parinol), 8- hydroxyquinoline (8-quinolinol), 8-hydroxyquinoline sulphate (quinosol), benzoyl-8-hydroxyquinoline salicylate, 3-( Z-methylpiperidino)propyl-3,4- dichlorobenzoate, 6-ethoxy-1,2-dihydr0-2,2,4- trimethylquinoline ethoiiyquin), N-laurylisoquinolinium bromide, 9-(para-n-hexyloxyphenyl)- IO-methylacridiniumchloride, and 9-(para-nhexyloxyphenyl l O-methylacridinium-para-toluene sulphonate; 2- and 3-N-heterocycles 6zinc -quinoxaline 2-n-heptadecylimidazolidine acetate (glyodine), lhydroxyethyl-Z-heptadecylimidazolidine, l-phenyl-3,5- dimethyl-4-nitrosopyrazole, 1-para-chlorophenyl-3',5- dimethyl-4-nitrosopyrazole, l-para-sulphamylphenyl- 3,5-dimethyl-4-nitrosopyrazole, N-( l-phenyl-2- nitropropyl)piperazine, 2-dimethylamino-6-methyl-5- n-butyl-4-hydroxypyrimid'ine,

tetrahydropyrimidine, N-dodecyl-Z-methyll ,4,5 ,6- tetrahydropyrimidine, 2-n-heptadecyltetrahydropyrimidine, l-( 4-amino-4-propyl-5- pyrimidylmethyl)-2-methylpyridinium chloride hydrochloride, 2-(2-furyl)-benzimidazole (furidazole), 3- dodecyl- 1 -methyl-2-phenylbenzimidazolium ferricyanide, methyl-N-benzimidazol-2-yl-N-( butylcarbamoyl)carbamate benomyl), 2-( ortho-chloroanilino) 4,6-dichloro-sym.-triazine, and 2-ethylamino-6-methyl- 5-n-butyl-4-hydroxypyrimidine; S-Heterocycles 5 -chloro-4-phenyll ,2-dithiol-3-one, 1,4-dithia-anthraquinone dithianone thiazolyl)-benzimidazole; NO-, NS- and OS-heterocycles 4-( 2-chlorophenylhydrazono)-3-methyl-5- isoxazolone drazoxolone), thiazolidinone-4-thione- 2) rhodanine), 3-( parachlorophenyl)-5- methylrhodanine, 3 ,S-dimethyltetrahydro-l ,3 ,5- thiadiazine Z-thione (dazomet), 3,3-ethylene-bistetrahydro-4,6-dimethyl)-2H-1,3 ,S-thiadaZine-Z- thione) (milneb), 3-benzylidene-amino-4-phenylthiazoline-2-thione, 5-chlorobenzthiazole-2-thiol zinc salt, 6-B-diethylaminoethoxy-2-dimethylaminobenzthiazole dihydrochloride, monoethanolammonium-benzthiazole-Z-thiol, laurylpyridinium-S-chloro-2- mercaptobenzthiazole, zonc and sodium salts of 2- mercaptobenzthiazole and dimethyldithiocarbamate, 6-( B-diethylaminoethoxy )-2- 2,3-dicyanoand 2- 4- dimethylaminobenzthiaole dihydrochloride, 3 trichloromethylthiobenzolthiazolone 3- trichloromethylthiobenzoxazolone, 3- trichloromethyl)-5 -ethoxy-l ,2,4-thiadiazole, 6-

monium chloride, and benzoyltrimethylammonium bromide; Fungicidal antibiotics N-dodecyl- 1 ,4,5,6-'

9 Gliotoxin, 2,4-diguanidino-3,5 ,6-trihydroxycyclohexyl 5-deoxy-2-0-( 2-deoxy-2-methylamino-a-L- glucopyranosyl)3-C-formyl-B-L- hyxopentanofuranoside (streptomycin), 7-chloro-4,6- dimethoxycoumaran-3-one-2-spiro-1 2-methoxy-6'- methylcyclohex-Z-en-4-one) griseofulvin), 4- dimethylamino-l ,4,4a,5 ,5a,6,1 1 ,l2a-octahydro- 3 ,5,6, 1 O, l 2, 12a-hexahydroxy-6-methyll ,l l-dioxo-2- naphthacenecarboximide (oxytetracycline), 7-chloro- 4-dimethylamino-1,4,4a,5,5a,6,1 1,l2aoctahydro- 3,6,10,12,12a-pentahydroxy-6-methy1-l,11-dioxo-2- naphthacenecarboximide chlorotetracycline),

. (pimaricin), lancomycin), (phleomycin), (kasugamycin), (phytoactin), D(-)-threo-2,Z-dichloro-NJB- hydroxy-a-( hydroxymethyl)-para-nitrophenethyl- ]aretamide (chloramphenicol), and blasticidine-S- benzylaminobenzenesulphonate;

Miscellaneous substances tobenzthiazole mixture, zineb/mercaptobenzthiazole mixture, Zineb/nickel ll) chloride mixture, zineb/nickel(ll) sulphate mixture, ziram/basic copper sulphate mixture, ziram/zinc/mercaptobenithiazole mixture,

thiram/cadmium hydrochloride mixture, thiram/hydroxymercury chlorophenol mixture, thiram/phenylmercury acetate mixture, polyethylene/bis-thiouram sulphide/copper oxychloride mixture, methylarsine/bis-(dimethyl-dithiocarbamate)[ziram/thiram mixture, folpet/phenylmercury acetate mixture, dodine/ferham/sulphur mixture, diethianone/copper oxychloride mixture, dichlone/ferbam/sulphur mixture, dinocapldinitrooctylphenol mixture, captan/quintoiene/tribasic copper sulphate mixture, cadmium propionate/- phenylmercury propionate mixture, formaldehyde/urea mixture and phenylar'nmonium cadmium dilactate/phenylmercury formamide mixture.

The following examples illustrate but in no way limit the invention as hereinbefore described. Temperatures are given in degrees centigrade and parts by weight.

EXAMPLE 1 a. An amount of 230 g. of 2-bornylamine is dissolved in 1,000 ml. of absolute toluene; into this solution at 30-40 are fed 60 g. of dried hydrogen chloride gas, and into the obtained suspension at 100 are subsequently introduced 160 g. of dried phosgene within 5 hours. After cooling, the excess phosgene is removed by the passing through of a strong flow of air. The clear solution is concentrated in vacuo to dryness and the residue distilled. The 2-bornyl-isocyanate has the B.P.:

30 l02l04, 12 Torr; and M.P.: 65.

b. To a solution of 245 g. of 2-bornylisocyanate in Q 700 ml. of absolute tetrahydrofuran is added dropwise at a solution of 215 g. of 5-nonanone-oxime in 300 ml. of tetrahydrofuran. The clear solution is afterwards stirred for 5 hours at it is then allowed to cool before being concentrated in vacuo. The 0- (bornyl(2)-carbamoyl)-5-nonanone-oxime has the B.P.: 95-100 at 0.4 Torr. (Compound No l) The following compounds are prepared in a analo- 40 gous manner.

No. Compounds Physical data 2 o-(Dodecyl-carbamyl)-2-butanone-oxime B.P.: 127 136/0,03 3 O-(Dodecyl-carbamoyl)-4,4-dimethoxy-Z-butanone-oxime B.P.: 68 70 4 0-(Bornyl(2)-carbamoyl)4,4-dimethoxy-2-butanone-oxime B.P.: 67 72/0,03 5 0-( l,4-Menthyl(3)-carbamoyl)-3-heptanone oxime HP. 11: 62 64/0.l 6 O-(Borhylt 2)-carhamoy| )-2-nonanone-oxime B.P.: 64 67l0.1 7 0-( l,4Menthy|-3)-carbamoyl-3-heptanoneoxime B.P.: 69 /0,04 8 0-( 1,4-Menthyl(3)-curbamoyl)-2-)methyl?-ethyI-4-nonanone-oxamine B.P.: 82 /0.3 9 0,1 l,3,3-Trimethyl-norbonyl(2)-carb0rn0yl)-2-methyl-7-ethyl-4-nonu- B.P.: 77 78/0,04

none-oxime 10 0'1Docecyl-carbnmoyl)-5-nonanone-oxime B.P.: 170 [0.02 i 11 0t3,5,5-Trimethy1-cyclohexen(2)-yl-carbamoyl)-5-nonununeoxime B.P: 72 78/0,02

l2 0-( l,4Menthyl(3)-carbamoyl)-5-nonanone-oxime B.P.: 98 10270.02

13 0-[Bicyclo[4.1.0lheptylr 7)-carbumoyll-S-nonanone-oxime B.P.: 79 82/0.02

14 0-1 1,3.3-Trimethyl-norbonyl12)-carbamoy1)-5nonanone-oxime B.P.: 74 76/0.01

15 0-(Dodecyl-curbamoyl)-benzaidehyde-oxime M.P.: 67 69 16 0-1Dodecyl-carbumoyl)-4-chlorobenzaldehyde-oxime M.P.: 58

17 0-(Cyclohexyl-carbamoyl)-benzaldehyde-oxime M.P.: I28 130 18 0-(Cyclohexyl-carbamoyl)-4-chlorobenzaldehyde-oxime M.P.: 134 137 19 0-(Borny|(2)-carbamoy11-4-ch1orobenzaldehyde-oxime M.P.: 132 134 20 0 (Dodecyl-carbamoyl)-acetophenone-oxime M.P.: 59 61 21 0-(Cyclohexyl-carbamoyl)-acetophenone-oxime n,, 1.5495

22 0- l,3,3-Trimethyl-norbony1f2)-carbamoyl)-uceto-phen0ne-oxime B.P.: 78 B.P.: 78 X1/0.02

23 0-1Dodecyl-carbamoyl1-propi0-phenoneoxime M.P.: 68

24 0-1Bornyl(2)-carbamoyl)-propiophenone-oxime nondistillable oil 25 0-(1,4-Menthyl(3)-carbamoyl)4-phenyl-Z-butanone-oxime B.P.:]Ol /0.6

26 0( 1 ,3,3Trimethyl-norbornyl(2)-carbamoyl)-4-phenyl-Z-butanone-oxime M.P.: 1 17 27 0-(Bornyl(21-carbamoyl)-4-phenyl-2-butanone-oxime B.P.il l0 l l2/0.7

28 04Dodecyl-carbamoyl)-cyclopentanone-oxime M.P.: 48 50 29 0-(Cyclohexyl-carbamoyl)-cyclopentanone-oxime M.P.: 49 50 30 0-(3,5,S-Trimethyl-cyclohexeM2)-yl-carbamoyl)-cyclopennmonc-oximc M.P.: I I I 113 31 0-(1.4-Menthylt3)-carh;|moy|)cyclopentanonc-oxime M.P.: 97 100 34 0-(l,4-Menthyl13)czirbalmoyl)-cyclohexzlnone-oxime M.P.: 83 85 35 0-( l,3,3-Trimethyl norhornyl(2)-carbamoyl )-cyc|ohexunonc-oxime M.P.: 1 12 1 14 Continued N0. Compounds Physical data 36 ()-(Bornyl(2)-carbumoyl)-cyclohexnnone-oxime n,,'" 1.5103 37 -(3,5,5-Trimethyl-cyclohexen(2)-yl-curbamoyl)-cycloheptunoneoxime B.P.: 72 73/0.02 38 0-( l,4-Menthylt3)-carbamoyl)-cycloheptanone-oxime B.P.: l20/0.02 39 0-( l,3,3-Trimethyl-norbonyl(2) curbamoyl)-cycloheptanone-oxime M.P.: 85 87 40 0-IBicyclo[4.l.O]heptyl(7)-carbumoyll-cycloheptanoneoxime M.P.: 70 72 41 0-(Bornylt2)-carbamoyl)-cycloheptanone-oxime n,, 1.5092 42 (l-(Dodecyl-carbamoyl)-cyclododecanone-oxime n 1.48 30 43 0-( 1,3,3-Trimethyl-norbornyl(2)-carbumoyl)cyclododecanone-oxime M.P.: 133 135 44 (H l,4-Menthyll3)-carbamoyl)-l,4-menthone(3)-oxime B.P.: 87 89/0,2 45 0-(1,3.3-Trimethyl-norbornyl(2)-carbamoy1) 1,4-menthone(3)-oxime B.P.: 94 96/0,09 46 0-(Borny1(2)-carbamoyl)-l,4-menrhone(3)-oxime B.P.: 130 l35/0,5 47 0-(1,4-Menthylt3)-carbamoyl)-2-bornanone-oxime n 1.4984 48 0-( 1.3,3-Trimethyl-norbornyl(2)-carbamoyl)-2-bornanone-oxime M.P.: 152 155 49 0-(Bornylt2)-carbamoyl)-bornanone(2)-oxime M.P.: 181 184 50 0-( 1.3 ,3-Trimethyl-norbornyl( 2 )-carbamoyl )-tricyclo[2.2. l 0

3-heplanone-oxime B.P.: 126 130/0,2 51 0-( Bornylf 2)-curbamoyl )-tricyclo|2.2. l .O ]-3-heptanone-oxime n,, 1.5193 52 (HOctyl-curbamoyl)-bornanone (2)-oxime n 1.4895 53 0-(Decyl'carbamoyl)-bornunone (2)-oxime n 1.4867 54 0-1Dodecyl-carbamoyl)-bornanone (2)-oxime n,,'' 1.4861 55 U-(Tetradecyl-carbumoyl)-bornanone (2)-oxime M.P. 52 4 54 56 0-(Cyclohexyl-carbumoyl)-bornanone (2)-oxime n 1.5092 57 0-(Cyclooctyl-carbamoyl)-bornanone (2)-oxime n 1.51 19 58 0-(BenzyI-carbamoyl)-bornanone (2)-oxime M.P. 75 79 59 0-( 1,4-Menthyl (3)-carbumoyl)-tricyclol2.2.10

3-heptanone-oxime M.P. 131 132 EXAMPLE 2 A. Dusting agents For the preparation of a) a 10 percent dust, (b) a percent dust, and (c) a 2 percent dust, the following materials are used:

a. parts of 0-(3,5,5-trimethylcyclohexen(2)-ylcarbamoyl)-5-nonanone-oxime, No. 1 l 5 parts of highly dispersed silicic acid, 85 parts of talcum; b. 5 parts of 0-( 3,5,5-trimethylcyclohexen( 2)-ylcarbamoyl)-cycloheptanone-oxime,( No. 37)

95 parts of talcum;

2 parts of 0-( bornylt 2)-carbamoyl)-5-nonanoneoxime,

1 part of highly dispersed silicic acid, (No. l)

97 parts of talcum.

The above listed active substances are intimately mixed and ground with the carriers. The thus obtained fungicidal dusting agents are used for the treatment of the soil of seed beds, or for the dusting of plants.

B. Wettable powders The following constituents are used for the preparation of(a) a 50 percent, (b) a 40 percent, (0) a percent, and (d) a 10 percent wettable powder:

a. 50 parts of 0-(bicyclo[4.l.0]heptyl-carbamoyl)-' cycloheptanone-oxime, No. 40)

5 parts of naphthalenesulphonic acid-benzenesulphonic acid'formaldehyde condensate,

5 parts of dibutylnaphthalenesulphonic acid,

5 parts of Champagne chalk,

20 parts of silicic acid,

15 parts of kaolin;

40 parts of 0-( cyclohexyl-carbamoyl)-acetophenoneoxime,(No.2l)

1 part of dibutylnaphthalenesulphonic acid,

5 parts of ligninsulphonic acid-sodium salt,

2 parts of 1:1 mixture of Champagne chalk-and hydroxyethyl cellulose,

parts of kaolin,

22 parts of sodium-aluminium-silicate;

25 parts of 0-( bomylt 2)-carbamoyl)-5-nonanoneoxime,(No. l)

5 parts of oleyl methyl tauride sodium salt,

2.5 parts of naphthalenesulphonic acid-formaldehyde-condensate,

0.5 parts of carboxymethyl cellulose,

5 parts of neutral potassium aluminium silicate,

62 parts of talcum;

10 parts of 0-( 3,5,5-trimethylcyclohexen( 2)-ylcarbamoyl)-cycloheptanone-oxime, (No. 37)

3 parts of a mixture of the sodium salt of saturated fatty alcohol sulphates, 5 parts of naphthalenesulphonic acid-formaldehydecondensate, 82 parts of kaolin. The active substances are intimately mixed, in suitable mixers, with the additives, and then ground on suitable grinding mills and rollers. Wettable powders are thus obtained which can be diluted with water to form suspensions of any desired concentration; Such suspensions are used mainly for the protection of plants.

CQPaste The following materials are of a 45 percent paste:

45 parts of 0-( cyclohexyl-carbamoyl)-acetophenoneoxime,( No. 21) 5 parts of sodium aluminium silicate, 14 parts of cetyl polyglycol ether with 8 moles of ethylene oxide,

1 part of oleyl polyglycol ether with 5 moles of ethylene oxide,

2 parts of spindle oil,

10 parts of polyethylene glycol,

23 parts of water. i

used for the preparation The active substance is intimately mixed and ground,

in suitable equipment, with the additives. A paste is obtained, from which can be produced, by dilution'with water, suspensions of any desired concentration.'These suspensions are mainly used for plant protection.

D. Emulsion The following ingredients are mixed together for the preparation of a 10 percent emulsion concentrate:

EXAMPLE 3 Action against Botrytis cinerea on Vicia faba (broad beans) Petri dishes were lined with moist filter paper and into each dish were then placed three well developed and uniformly large leaves of Vicia faba; the leaves were subsequently sprayed until dripping wet with a liquor prepared from the active substance in the form of EXAMPLE 4 Action on Erysiphe cichoracearum (powdery mildew of cucumbers) on cucumbers (Cucumis sativus) Young cucumber plants were sprayed dripping wet with a 1 percent suspension'of the active substances formulated as wettable powder. When the plants were again dry they were infected with a spore suspension of powdery mildew of cucumbers, and subsequently placed in a green-house at ca. 23. After 8 days the. degree of infection proportion of leaf-surface covered by fungal coating) on the infected treated leaves compared with that on infected untreated control specimens is determined.

The interpretation of the numbers appearing in the following table is given below:

9-1 linear decrease in degree of infection;

no infection.

' known from the French Patent Specification No. 1.549190 wettable powder 0.1 percent active substance content). After the leaves had again become dry they were infected with a freshly prepared fungi spore suspension and kept for 1-2 days in a moist atmosphere at 10 ineffective, infection equally as severe as inthe case of the untreated control plants;

" EXAMHFS Action against Phytophthora infeszans blighton leaves and tubers) on tomatoes Solarium lycop er sicum) Tomatoes of the same type and in an identical stage of development were sprayed with a liquorof0.l percent of active substance (prepared from the active substance processed into the form of a wettable powder). When the tomatoes were again dry theywere' infected with a spore suspension of Phytophthora infestans and kept for about 6 days in a green-house at l820 with a high level of atmospheric moisture -100 percent). After this period they exhibit typical leaf spots. Anassessment of the tested substances was: made on the 9-1 linear decrease in infection;

0 no infection. basis of the number and size of the leaf spots.

No. Compound 3! (H I,4-Methylt3)-carbamoyl)-cyclopentanone-oxime 3 3O 04 3.5.S-Trimethyl-cyclohexent 2)-yl-carbamoyl)- l cyclopentanone-oxime 37 0-( 3.5,S-Trimethyl-cyclohexeM 2)-yl-carbamoyl 2 cycloheptanone-oxime 2 0-( Dodecyl-carbamoyl )-2-butanone-oxime 0 3 (H Dodecyl-carbamoyl)-4,4-dimethoxy-Lbutanone-oxime 3 42 (HDodecyl'carbamoyl)-cyclododecanone-oxime l 20 0-( Dodecyl-carbamoyl)-acetophenone-oxime O 4 0-r Bornyl(2)-carbamoyl)-4.4-dimethoxy-2-butanone-' 4 oxime 32 U-( Bornyll 2 )-carbamoyl )-c'yclopentanone-oxime 0 36 0-( Bornylf2)-carbamoyl)-cyclohexanone-oxime 0 4| O-( Bornylt2)-carbamoyl)-cycloheptanone-oxime 2 35 (H l.3.3-Trimethyl-norbornyl(2)-carbamoyl)-cyclo- 3 hexanone-oxime 39 04 l.3,B-Trimethyl-norbornylt2)-carbamoyl)-cyclo- 3 heptanoneoxime l7 O-tCyclohexyl-carbamoyl)-benzaIdehyde-oxime 3 0-( Octahydro-l .2,4-methenopentalenyl( 5 )-carbamoyl)- l0 propiophenone* 0-( Octahydrol .2,4-methenopentalenyl( 5 carbamoyl)- 8 5-nonanone-oxime* known from the French Patent Specification No. 1.549.790

The interpretation of the numbers appearing in the following table is given below:

I ineffective, infection equal to that on the untreated control plants;

tive substance respectively in the form of a aque ous suspension. 24 hours after this treatment each plant was mechanically inoculated. The evaluation of the results was carried out one week later and may be sumav 9l linear decrease in degree of infection;

0 no i f ti Med as follows:

No. Compound 49 0-(Bornyl(2)-carbamoyl)-2-bornanone-oxime 4 2 l (H CycIohexyl-carbamoyl)-acetophenone-oxime 4 5 0-( l.4-Menthyl(3)-carbamoyl)-2-nonanone-oxime 4 44 0-( l,4,-Menthyl(3)-carbamoyl)-l,4-menthon-(3)-oxime 4 EXAMPLE 6 N 0. Compound cone. value In) Action on Uromyces appendzculates (bean rust) on beans Phaseolus vulgaris) l8 O-lCyclogefiyl-carbamoyl)-4-chloro- I; benzalde y e-oxime lBean plants n the two leaf stage were sprayed until 33 (H3Y3,sxflmethybcydohexem5) yl 1000 7 II m we W! a SUS 61181011 0 (2 ac we su S ances carbamo )-cyco exanone-oxime d pg t th fth t bt yl lh 2000 2 made up as wettable powder conc. 0.1 percent of ac- 0 34 2'g i'gggt gg gf g' ;3% a .tive substance). When the plants were again dry they 47 i" r 1083 3 were infected with a freshl re ared bean rust s ore bomanone(2)-0Xim.e

- 5 l y p d k f 48 0-( l,3,3-Trimethyl-norbornyl(2)- l000 4 suspenslo n p ants per Pro an ept or ay carbamoyl)-bornanone(2)-oxime 2000 2 in a moist chamber and then m a green-house at 49 0-(Bornyl(2)-carbamoyl)-bornanone- ;g% 2 2022. Evaluation of the test results is based on the number of rust spots present after about 8-12 days. The numbers in the following table have the meanineffective, infection q y severe b untreated control plants; mgs gwen e 9-1 linear decrease in degree of infection;

[0 ineffective, infection equally as severe as that on 0 Infection the untreated control plants; 9-] linear decrease in degree of infection; 0 no infection.

No. Compound 1 l (H 3.5,S-Trimethyl-cyclohexent 2)-yl-carbamoyl 5nonanoneoxime 4 0-( Bicyclol4. l .Olheptyl-carbamoyl)-cycloheptanoneoxime 0 l7 0-( Cyclohexyl-carbamoyl)-benzaldehyde-oxime 0 18 O-( Cyclohexyl-carbamoyl)-4-chlor-benzaldehyde-oxime l 0-( Octahydro-l ,2.4-methenopentalenyl( 5 )-carbamoyl)- propiophenone-oxime* l0 0-( Octahydro-l .2,4-methenopentalenyl( 5 )-carbamoyl)- cyclohexanone-oxime* l0 known from the French Patent Specification No, l,549 790 wharaaaaia r. W k

l. A carbamoyloxime of the formula Rr=NO(l..INHR| EXAMPLE 7 50 Action against Potato Virus-Y on pepper (Capsicum wherein R is bornylidene or norbornylidene, and R is annuum) bornyl or 1,3,3-trimethylnorbornyl Two separate groups of 15 pepper plants were 2. 0-( l,3,3-Tr|methyl-norbomyl( 2)-carbamoyl)- sprayed 3 days after unfolding of the seedling leaves, 2bornanone oxlme. with solutions containing 1,000 and 2,000 ppm of ac- 3. 0-(Bornyl(2)-carbamoyl)-2-bornanone oxime.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION e PATENT NO. 3,843,724

DATED October 22, 1974 'INVENIOR(S) Karl Gatzi It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below: 0

Title page, item I30]: change "Jan. 14, 1971" to March 23,

a I d Engnc and Sealed tlus I twenty-sixth Day Of August 1975 [SEAL] I Arrest:

RUTH C. MASON C. MARSHALL DANN 'A C K ffI'P (ommisxr'mzer nj'larents and Trademarks 

1. A CARBAMOYLOXIME OF THE FORMULA R5=N-OOC-NH-R6 WHEREIN R2 IS BORNYLIDENE OR NORBORNYLIDENE, AND R6 IS BORNYL OR 1,3,3-TRIMETHYLNORBORNYL.
 2. 0-(1,3,3-Trimethyl-norbornyl(2)-carbamoyl)-2bornanone oxime.
 3. 0-(Bornyl(2)-carbamoyl)-2-bornanone oxime. 